Process for the manufactur of boron nitride



April 29, 1958 G. H. FETTERLEY ETA).

PROCESS FOR THE MANUFAOTURE OF BORON NITRIOE Original Filed Sept. 16, 1953 PRCESS FOR THE MANUFACTURE F BORN NlTRlDE Guy Fetterley and George R. Watson, Chippawa, 0ntario, Canada, assignors to Norton Company, Worcester, Mass., a corporation of Massachusetts Original lapplication September 16, 1953, Serial No. 380,472, now VPatent No. 2,801,903, dated August 6, 1957. Divided and this application December 2, 1954, Serial No. 472,612

1 Claim. (Cl. 22S-191) The invention relates to boron nitride and provides .an improved process for the manufacture thereof. vThis application is a division of our copending application Serial No. 380,472 filed September 16, 1953, now Patent No. 2,801,903, which was a continuation-in-part of our copending application Serial No. 243,704, filed August 25, 1951, now abandoned.

One object of the invention is to provide a cheap process for the manufacture of boron nitride. Another object is to produce a relatively pure grade of boron nitride. Another object is to provide a process which will not plug up the apparatus used. Another object is to provide a process which can be carried out with very simple apparatus. Another object of the invention is to produce boron nitride in a continuous process. Another object is to produce insoluble boron nitride in a continuous process. Another object is to produce boron nitride with the recovery of hydrochloric acid as a by-product. Another object is to provide apparatus for theproduction of boron nitride which will not quickly corrode.

Another object of the invention is to provide a method for molding boron nitride. Another object of the invention is to provide solid pieces of dense boron nitride which previously have been non-existent. Another object of the invention is to provide a method for molding boron and also for molding boron carbideihaving more boron therein than is represented by the formula B5C. Another object of the invention is to provide solid pieces of boron carbide 'having more boron than is represented by the formula B5C and to provide solid pieces of `relatively pure boron. Previously it was impossible to make molded boron carbidehaving substantially more `boron therein than is represented by the formula B5C because `boron carbide had to be molded in graphite molds orin carbon molds and if such boron carbide had less carbon than is represented by the formula B5C it would pick up enough carbon from the mold to produce pieces having '.as much carbon therein as is represented by the formula B4'C or nearly so much thereof. For the same reason therefore it was previously impossible to produce molded pieces of boron because the only known way to mold .boron was to mold it in a graphite or in a `car-bon mold and such boron being so molded would pick up carbon to produce boron carbide having almost, if not quite, as much carbon as is represented by the formula B4G.

Other objects will be in part obvious or in VVpart pointed out hereinafter.

The accompanying drawings illustrate apparatus which can be used to carry out the process of the invention.

The equipment consists of three operating units, which are listed below:

(1) A low temperature (900 C.) reactor in which chlorine and boron carbide react vto .form boron trichloride and carbon.

(2) A high temperature (l600-2200 C.) reactor in which boron trichloride and ammonia Areact to form solid finely divided BN suspended in a stream of gaseous 'byproducts.

te States Patent '2,832,672 Patented Apr. 29, 1958 rice Yprovide a controlledsource of dry chlorine, which is-led into the reactor by an inconel pipe 12. The pipe 12 is screwed into a tapped hole in the gnaphite plug 13 'at the inlet end of graphite tube 15. At the outlet end of the graphite tube 15 is a graphite plug 16, into which passes a small mild steel tube 17. While dimensions are not critical, a graphite tube 15 that is three inches in inside -diameter and three feet -long is convenient and readily available.

The graphite tube 15 is packed with crude boron carbide in the form of roughly crushedl lumps or grain. It is heated by a coil lof resistance wire insulated I'from the tube by a few layers of asbestos paper and refractory cement and ending -in leads 18 and 19. As indicated in the drawing the 'temperature valong the central part of the tube is about 900 C. vand the bulk ofthe boron carbide is heated to this temperature. The reaction between chlorine and boron carbide is represented by the following equation,

,graphite tube 21 screws into the inside face .of the plug .22 `and extendsseveral inches, ksuch as -iive inches, into the tube 23 beyond the plug .22. The temperature at the exit end of the tube 21 is about 500 C. The graphite tube 23 is heated by an electric current at low voltage ang high amper-age through the water-cooled electrode clamps and bus bars 24 and r25, and itstemperature is measured atl intervals with an optical .pyrometer.

Weprovide a second'hole in the graphite'plug 22 at the inlet end of the main tube 23 ofthe high temperature reactor, through which we introduce gaseous ammonia Aby means of va mild steel pipe 26 that `is screwed into a tapped. hole in the plug 22. Note that thetwo gaseous reactants are introduced at separate pointsV to avoid plugging by boron nitride and by ammonium chloride condensed by the cool entering gases. Thus boron trichloride and ammonia meet, mix, and begin to react at a lpoint in the tube 23 that is at a temperature offabout500 fC. Any .leaks at the end of .the tube are quickly plugged by condensed ammonium chloride. 'The gaseous mixture advances through the tube `Z3,.encountering a series of graphite bafes 30 having holes 31, to produce turbulence. These baffles Stlare located at vabout the centre of the tube 23 lengthwise, and in this zone the temperature lis preferably about 2000 C. Pour baies are shown .but the number is not critical.

A series of reactions occur in the tube 23. Thesejreactions maybe represented by the following equations:

(Decomposition of borumide into bormde. and ammonia) (Decomposition of borimide into boron-nitride and ammonia) .By refinements in reactor design it might be possible'to use much of the ammonia generated by Reactions 2 and 3 to react with fresh boron trichloride by Reaction Al. If lall the'theoretically available ammonia 'were used up Vindicated by Equation 5.

v quantity of ammonium chloride vapor.

in this way, the overall chemical change taking place in the furnace could be represented by the following equation:

' BCl3-l-NH3=BN+3HC1 (4) lf none of the ammonia generated by Reactions 2 and 3 is available for reaction with fresh boron trichloride, the overall chemical change is represented by the following equation:

2NH4Cl=2NH3+2HCl=N2l3H2+2HCl (6) Since all the by-products on the right are non-condensing gases, boron nitride is the chief solid product of the reaction and is easily collected in a filter. The exit end of the reactor tube 23 is fitted with a graphite plug 33. To avoid the formation of drifts of powdered boron nitride, a short pipe of large diameter 32 leads to a standard commercial filter 41 which uses woven glass cloth 42 as a filtering medium to resist the corroding etect of hot hydrogen chloride. The connecting pipe 32 can be a section of standard steel pipe, but should be the formation of volatile iron chlorides that may find their way into the product.

It is necessary to operate the high temperature reactor with a slight excess of ammonia. lf this precaution is not taken, some of the relatively costly boron trichloride remains unused. An even worse result is that some of the unused boron trichloride is adsorbed by the finely divided boron nitride, is eventually hydrolyzed by atmospheric moisture, and leaves an undesirable residue of boric acid in the boron nitride as an impurity. T here is no danger of this result if we use as much ammonia as lf the reactor operates with a long entry zone at a temperature below 1000 C. and with considerable turbulence in this zone, much of the ammonia released by Equations 2 and 3 will be recovered, and the ammonia ow to the reactor can be reduced. In each individual case the operator will have to adjust the ammonia flow to obtain a good yield, and since ammonia is cheap, it is usually best to work with a fairly large excess of it.

Evidently the gases leaving the high temperature reactor consist of hydrogen chloride and a variable amount of nitrogen and hydrogen. They carry in suspension nely divided boron nitride and a` variable amount of solid ammonium chloride. The filter illustrated having the woven glass cloth 42 catches 60%-80% of the boron nitride. After running the process for a length of time calculated to deposit the desired amount of boron nitride in the filter 41, the full ilter can readily be replaced with an empty one without stopping the process. It is possible to recover the hydrogen chloride from the waste gases in a scrubber to make hydrochloric acid, and to burn the residual gases, which are rich in hydrogen, as a fuel.

In the high temperature'reactor there is a considerable This vapor begins to condense at any temperature below about 500 C., forming a white glassy solid that quickly plugs the apparatus and renders it completely inoperative. lt is therefore very desirable to maintain a temperature of at least 480 C. at every point inthe high temperature kept cool by an air blast or by water cooling to avoid reactor where free passage of gases is desired. We note that this property of ammonium chloride is advantageous in one way, since the glassy condensate very quickly seals any leaks that may appear around the graphite plugs 22 and 23.

If the so-called high temperature reactor is operated at temperature below about 1600 C., Reaction 6 becomes slower. In fact, the lower the temperature, the more slowly Reaction 6 proceeds, and the more ammonium chloride vapor there will be in the gases leaving the furnace. If the lter is operated at a temperature below 500 C. some or all of the ammonium chloride will condense a-nd appear as a contaminant in the boron nitride. It is difficult to design a filter that will operate effectively at 500 C. or higher, and it is also very diliicult to replace a full lter heated to this temperature with an empty one without oxidizing some of the boron nitride by exposure to the air. So therefore we prefer to operate the filter at temperatures well below 500 C. preferably below C. and, in order to keep the ammonium chloride content as low as possible, the temperature somewhere in the high temperature reactor where the gases pass should be at least 1600 C. Too much ammonium chloride results in plugging of the apparatus.

We have found that, in order to obtain a very high purity boron nitride the product collected by the filter should be tired preferably up to about 2000 C. although firing it at 1000" C. greatly beneiiciates it. For tiring the boron nitride we pack it in a graphite mold, seal the ends of the mold with graphite plugs and place the mold in a furnace. The furnace described and illustrated in U. S. Letters Patent No. 2,125,588 to Ridgway can be used and it is not necessary to use pressure, but if pressure is used the product will be a solid piece of boron nitride. This step converts most of the boramide and/ or borimide to boron nitride and drives ot the content of HC1 and NH4C1.

The firing of the product collected in the filter makes the boron nitride resistant to moisture and without this step it decomposes in moist air. Because it volatilizes residual impurities and converts any residual boramide and/or borimide to boron nitride, we have succeeded in producing boron nitride at least 98% pure.

The surprising fact is that pure or nearly pure boron nitride cannot be hot molded to as high a density as the impure boron nitride taken directly from the tilter. This latter material can be hot molded into solid pieces of near theoretical density at pressures of at least 500 pounds to the square inch (there is no upper limit if the mold is strong enough) and at a temperature of at least l600 C. and not greater than 2300 C. Thus we have invented a process for the molding of boron nitride which, being an unctuous powder, could not previously be molded to zero porosity. Our molded boron nitride has a purity of better than 98% by weight since the hot molding operation is also a tiring operation.

Molded boron nitride has one very important use in that, if made into a mold, it can be used to mold lboron carbide having more boron than is represented by the formula B4G and it also can be used to mold relatively pure boron without adding any carbon to the product. As previouslyexplained such compositions could not heretofore -be molded without conversion of the product to substantially B4G. In order to make such a mold we simply make a sleeve of boron nitride by the technique fully described in U. S. Patent No. 2,535,180 issued on application of one of us, to wit, George R. Watson. This patent fully described the apparatus and method of hot pressure molding refractory material which can be ,so molded. Making a thin boron nitride sleeve according to the technique of the aforesaid Watson patent we also make boron nitride mold plungers by the technique described in Ridgways aforesaidV Patent No. 2,125,588,

insert the sleeve into an outer sleeve of graphite, there being a press t between the two, insert the powder to be molded inside vof the boron nitride sleeve, place the boron nitride plungers inthe ends of the hollow cylindrical mold thus made (these should t the boron nitride with a close sliding t) and then place this assembly in the molding furnace of Patent No. 2,125,588 and mold with a pressure of at least 500 pounds and at a temperature between 1600 C. and 2300" C. With regard to the pressure in this case and in all other cases mentioned in this specification the preferred ypressure is the standard pressure used with this furnace which is 2500 pounds per square inch.

Boron nitride is a white unctuous powder. Its practical applications at present include:

(a) Anti-sticking agent for glass makers molds. (b) Component in rectifying tubes.

(c) Crucible linings and lip coatings.

(d) Insulation for induction furnaces.

However, as heretofore made, it has recently required a selling price of around one hundred twenty-five dollars a pound which has considerably restricted its use. Since it is refractory (melting point about 2730" C.) and is inert in many processes it should have wider application at lower prices. We do not have exact cost gures for our process but are confident it can be made thereby and sold (yielding a profit) at prices well below one hundred twenty-five dollars a pound.

Boron trichloride is an expensive gas when bought in bottles on the open market. By avoiding the steps of condensing, redistilling and storing the boron trichloride and instead using it up as fast as it is made, great economy is achieved. Chlorine gas in bottles is relatively cheap and we can use a low grade of boron carbide or even boron carbide old furnace mix, both of which are relatively inexpensive and readily available at electric furnace plants where boron carbide is made. The boron carbide that we use in our process does not have to be (although it can be) B4G. Excess boron or excess carbon in the boron carbide (as compared with B4C) in nowise interferes with our process. We are only concerned with the total amount of boron in the boron carbide that we use and practically all of it will combine with the chlorine at 900 C. leaving graphite as pseudomorphs of boron carbide. It should be added that our third primary reactant, ammonia, is relatively cheap in bottles.

One feature of the invention is the use of a graphite container (the tube 23) in which to-carry out the second reaction and also the use of a graphite container (the tube in which to carry out the rst reaction. Ammonia and boron trichloride are highly corrosive at high temperatures but graphite will withstand them for a relatively long time. Furthermore graphite tubes are cheap. We can provide removable graphite or boron carbide liners in either or both of the tubes 23 and 15 to avoid replacement problems for a long time.

The chlorine and ammonia bottles can be replaced while the process is going on and even the exhaustion of the boron carbide in the tube 15 need not stop the process as another tube 15 charged with boron carbide and preheated to the desired temperature can be quickly substituted for the exhausted tube 15.

While we have given 900 C. as the optimum temperature for the reaction zone in the tube 15, this can be varied. We have successfully operated the process with the temperature in the tube 15 as low as 300 C., but we obtained much better yields with the inside of the tube 15 at about 900 C. We have mentioned graphite molds.

However carbon molds can he used. Graphite is, in avery real sense, carbon. All carbon, however, is not graphite. Either material can be used in any part of our process. Graphite is la little more resistant so we prefer it but it is also more expensive.

Example I As an example of the process of manufacture, a typical run with the equipment illustrated in the drawing is de- `scribed below. The tube L15 .through the -low temperature reactor was three inches inside diameter and two feet long. lThis tube was filled with boron carbide crushed so it would pass through yaY sieve having four openings `per lineal inch. This reactor 'was maintained at a temperature of 900 C. The tube 23 through the high temperature reactor was three inches inside diameter and four feet long. It was maintained at 2000 C. by measuring its temperature with an optical pyrometer through the lgraphite sight tube shown on the drawing.

Chlorine was introduced into the low temperature Ireactor through pipe 12 and t-he boron trichloride produced entered the high temperature reactor through pipe 20. Ammonia entered through pipe 2,6. The following were the feed rates:

These proportions provided about l0 percent more ammonia than required for the reaction The excess ammonia eliminated the possibility of any unreacted boron trichloride getting into the product, where it would react with atmospheric moisture to form boric acid. The latter material would have constituted a solid impurity in the product. This excess ammonia also made certain that none of the comparatively costly boron trichloride was wasted.

The yield of boron nitride averaged 60%-S0% of theoretical. Much `of it was less than one micron kin particle diameter and twould have been lost if ythe lter had not been extremely effective. We used a finely woven glass iilterbag in flter.41 and a net yield of about 1.5 grams per minute was obtained.

The product caught in thetilter contained about 37% boron and 47% nitrogen. In orderto obtain avery high purity boron nitride the product collected by the filter was red at 2000 C. :for 30 minutes. This lwas done by packing the boron nitride in a graphite mold, sealing the ends of the mold with graphite plugs and placing the mold in a Ridgway furnace `(U. S. Letters Patent No. 2,125,588). The mold was .provided with vent holes to enable volatile materialto escape. .The product from this firingoperation contained .about.44.1 .percent boron and 55.4 percent nitrogen.

Example AIl As a specific example of the hot 4pressing of boron vnitride we made :a solid cylinder kof boron nitride one inch in diameter-and one inch long. A graphite mold three inches longwith -a bore one inch indiameter was provided together with two graphite rods or plungers one inch in diameter and three inches long. One such plunger was inserted in the hole in the mold to act as a plug so the boron nitride powder could be held within the bore of the mold. The mold cavity was then filled Iwith boron nitride. Theoretical density was desired and we used the relatively impure product caught in the filter 41 shown in the drawing. If the red boron nitride were used for hot pressing the end product would be -well formed and strong, but it would contain about 10 Vto 15 percent pores. We therefore prefer to use the product as it comes from the lter (37% B, 47% N). To make a piece one inch diameter and one inch lon-g, 35 grams of this product was poured into the mold cavity. The other plunger was then inserted and the loaded mold assembly placed in a Ridgway furnace. The furnace ternperature was raised slowly to 1850 C. while a pressure of 2500 pounds per square inch was applied to the plungers. After about 20 minutes no further inward movement of the plungers took place. The mold was removed from the furnace when it was cool and the molded piece of boron nitride was then pressed out of lthe -graphite mold. Its weight was found to be about 28 grams and its density corresponded to about 2.2 grams per cubic centimeter which is the theoretical density of boron nitride.

Example III As an illustrative example of hot pressing a boron article, we made a disc of boron one half inch in diameter by one-eighth inch thick. It was desired that there be substantially no carbon in the end product and therefore a boron nitride mold was used for the operation. A boron nitride 1cylinder about one inch in diameter or larger with a one-half inch hole in it `was fabricated by procdure as in Example Il. `It had an overall length of about three-quarters of an inch, Hot-pressed boron nitride plungers were provided as well by procedure as in Example Il. This mold assembly was filled with the desired quantity of boron powder (0.92 gram) which was then hot pressed by procedure similar to that described for hot pressing the boron nitride. Because the boron was in contact only Awith boron nitride, the amount of carbon contamination was negligible. The boron article was pressed to theoretical density by applying 2500 pounds per square inch to the plungers of the mold assembly while maintaining the temperature of the mold at 1800 C. for minutes.

The Aboron disc when removed from the boron nitride mold was found to be formed and of nearly theoretical density (2.3 grams/cubic centimeter).

The intermediate product which is the impure boron nitride caught in the filter 41 consists of boron nitride plus boramide and/or borimide and also some ammonium chloride and possibly some occluded hydrogen chloride. We are utterly unable to give the percentage of boramide and borimide or to distinguish between the nitrogen in the boron nitride and in the ammonia or between the hydrogen in the boramide, the borimide, the hydrogen chloride and the ammonium chloride nor between the chlorine in the hydrogen chloride and in the ammonium chloride. All we can say is that the material caughtin the lter 41 before tiring has a boron plus nitrogen content of at least 50%, the nitrogen content 'being at least sufficient to combine with all of the boron to form the compound BN, the balance of the composition over and above the total boron and nitrogen being, except for less than one percent of other elements, al1 hydrogen and chlorine. However we do know that this material before ring is not unctuous and is not useful as a lubricant whereas the tired product is unctuous and is useful as a lubricant. The fired product we feel confident is at least 97% BN.

But, and this is surprising, it is the uniired product caught in the lter 41 which makes the best hot pressed boron nitride articles. Of course the hot pressing operation is in itself a tiring operation: the temperature of l850 C. is adequate to eliminate any hydrogen chloride, any boramide, any borimide and also the ,ammonium chloride.

The product collected in the ilter 41 can be red at as low as 1600 C. to beneciate it and make it unctuous. We usually prefer not to use temperatures above 2200 C. for this purpose.

It will thus be seen that there has been provided by this invention a process for the manufacture of boron nitride, a process for the molding of boron nitride, a process for the molding of boron, a process for the molding of boron carbide having at least as much boron as B5C, molded boron nitride, molded boron, and molded boron carbide having at least as much boron as B5C in which the various objects hereinbefore set forth together with many thoroughly practical advantages are successfully achieved. As various possible embodiments may be made of the mechanical features of the above invention |and as the art herein described might be varied in various parts, all without departing from the scope of the invention, it is to be understood that all matter hereinbefore set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.

We claim:

Process for molding boron nitride which `comprises placing in a mold a powder derived from the reaction of boron trichloride 'and ammonia which powder essentially consists of boron 'nitride in admixture with material selected from the group consisting of boramide and borimide and mixtures thereof and with material selected from the group consisting of ammonium chloride and hydrogen chloride and mixtures thereof, said powder having a boron plus nitrogen content of at least the nitrogen content being 'at least sufficient to combine with all of the boron to form the compound BN, the balance of the composition over and above the total boron and nitrogen being, except for less than one percent of other material, all` hydrogen and chlorine in combined states, said mold being made of carbon, pressing with a pressure of at least 500 pounds per square inch and at a temperature between 1600 C. and 2300 C.

References Cited in the file of this patent UNITED STATES PATENTS 896,341 Whitney Aug. 18, 1908 1,157,271 Weintraub Oct. 19, 1915 1,951,133 De Bats Mar. 13, 1934 FOREIGN PATENTS 12,377 Great Britain Ian. 22, 1914 483,201 Great Britain Apr. 13, 1938 v OTHER REFERENCES Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 8, pages 109-110. 

